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Radical and Nitrenoid Reactivity of 3-Halo-3-phenyldiazirines

2016; American Chemical Society; Volume: 18; Issue: 15 Linguagem: Inglês

10.1021/acs.orglett.6b01753

1523-7060

Rafael Navrátil, Ján Tarábek, Igor Linhart, Tomáš Martinů,

Phenothiazines and Benzothiazines Synthesis and Activities

3-Halo-3-phenyl-3H-diazirines (halogen = Br or Cl) undergo a dissociative single-electron transfer from alkyllithiums (RLi) in THF-based solvent mixtures. The resulting 3-phenyldiazirinyl radical, observed by EPR spectroscopy, is eventually transformed to benzonitrile. In Et2O, 2 equiv of RLi add to both nitrogens of halodiazirine N═N bond, affording N,N'-dialkylbenzamidines. The nitrenoid reactivity of some N-alkyl-1H-diazirine intermediates is manifested by their insertion into the α-C-H bond of THF or Et2O.